Alloyed anode materials for lithium-ion batteries (LIBs) usually suffer from considerable capacity losses during charge-discharge process. Herein, insitu-grown germanium clusters are homogeneously encapsulated into porous nitrogen-doped carbon nanofibers (N-CNFs) to form Ge/N-CNFs hybrids, using a facile electrospinning method followed by thermal treatment. When used as anode in LIBs, the Ge/N-CNFs hybrids exhibit excellent lithium storage performance in terms of specific capacity, cycling stability, and rate capability. The excellent electrochemical properties can be attributed to the unique structural features: the distribution of the germanium clusters, porous carbon nanofibers, and GeN chemical bonds all contribute to alleviating the large volume changes of germanium during the discharge-charge process, while at same time the unique porous N-CNFs not only increase the contact area between the electrode and the electrolyte, but also the conductivity of the hybrid.